EP2495066B1 - Stainless steel flux-cored wire - Google Patents

Stainless steel flux-cored wire Download PDF

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Publication number
EP2495066B1
EP2495066B1 EP12000432.0A EP12000432A EP2495066B1 EP 2495066 B1 EP2495066 B1 EP 2495066B1 EP 12000432 A EP12000432 A EP 12000432A EP 2495066 B1 EP2495066 B1 EP 2495066B1
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EP
European Patent Office
Prior art keywords
mass
hexavalent chromium
amount
fume
terms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12000432.0A
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German (de)
English (en)
French (fr)
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EP2495066A1 (en
Inventor
Hiroshi Sugahara
Tetsunao Ikeda
Hirohisa Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kobe Steel Ltd
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Kobe Steel Ltd
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Publication of EP2495066A1 publication Critical patent/EP2495066A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • B23K35/0266—Rods, electrodes, wires flux-cored
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362—Selection of compositions of fluxes

Definitions

  • the present invention relates to a stainless steel flux-cored wire for arc welding filled up with flux in an outer sheath made of stainless steel, and relates specifically to a stainless steel flux-cored wire suppressing the amount of hexavalent chromium included in fume generated in welding stainless steel.
  • Cr is included by 10 mass% or more, and when the slag and fume are dumped to soil and the like as they are and left for a long period of time, there is a problem that Cr may possibly be eluted into the soil and the like as hexavalent chromium (Cr 6+ ).
  • a flux-cored wire which contains Si: 1.0-4.0 mass% and Cr: 16-30 mass%, and Si/(Ti+Zr) is 0.8 or above and (Na+K) ⁇ Cr 2 is 50 or below.
  • a wire for welding stainless steel which, in order to suppress elution of hexavalent chromium from slag, contains Cr: 12-32 mass%, N: 0.005-0.06 mass%, Ca: 0.01 mass% or below, Na: 0.01-0.5 mass%, K: 0.01-0.5 mass%, Na+K: 0.01-0.5 mass%. Also, in this document, it is disclosed that the wire is annealed by hydrogen gas in the manufacturing process of the wire.
  • hexavalent chromium in fume is analyzed by the diphenyl carbazide absorption method after extraction treatment by distilled water, however when the analytical method of ISO 16740:2005 is employed, even when the composition is in the range described above, there is a case that sufficient hexavalent chromium reduction effect cannot be secured. Further, because the weldability also has not reached a practical level, these flux-cored wires have not been practically used.
  • the flux-cored wire for welding stainless steel described in Japanese Published Unexamined Patent Application No. 2009-154183 aims to reduce hexavalent chromium in slag, and has a problem that it is not effective in reducing hexavalent chromium in fume.
  • the present invention has been developed in view of such problems and its object is to provide a stainless steel flux-cored wire capable of reducing the amount of hexavalent chromium in fume compared with conventional cases even when an analytical method in accordance with ISO 16740:2005 is employed while maintaining excellent weldability.
  • the stainless steel flux-cored wire in relation with the present invention is a flux-cored wire for arc welding filled up with flux in an outer sheath made of stainless steel containing, as percentage to the total mass of the wire:
  • Na compound, K compound and Li compound 0.50 mass% or below in total of each of an amount in terms of Na [Na], an amount in terms of K [K] and an amount in terms of Li [Li]; wherein: 50 ⁇ Ni + Mo + Mn + Fe ⁇ 80, where [Ni] represents Ni content, [Mo] Mo content, [Mn] Mn content and [Fe] Fe content; and Na + K + Li ⁇ Cr 2 / Si + 4.7 ⁇ F ⁇ 10 is satisfied where [Cr] represents Cr content.
  • the amount in terms of each element means an amount converted to the content of the mass which only the element occupies when a content of a compound is to be calculated.
  • the amount of hexavalent chromium in fume can be reduced while maintaining the weldability excellent. Also, because the flux-cored wire according to the present invention contains TiO 2 : 1.5 mass% to 8.0 mass% and ZrO 2 +Al 2 O 3 : 0.1 mass% to 3.2 mass% as percentage to the total mass of the wire, excellent arc stability and slag removability are maintained.
  • FIG. 1 is a graph showing the relation between Na + K + Li ⁇ Cr 2 / Si + 4.7 ⁇ F and the amount of hexavalent chromium in fume.
  • the flux-cored wire has spread to wide fields because it has excellent weldability and high performance. Particularly in the welding material for stainless steel, the use ratio of the flux-cored wire is high. However, in the fume generated in welding using a conventional flux-cored wire for welding stainless steel, Cr is contained by 10 mass% or above, and a part of the Cr is present in the form of hexavalent chromium.
  • a stainless steel flux-cored wire has been developed which reduced hexavalent chromium in fume while maintaining excellent weldability.
  • Cr content which is an indispensable element for stainless steel is below 11 mass%, a passive film is not formed and the corrosion resistance required for the weld metal as a welding wire for welding stainless steel is not exerted. Also, when the Cr amount exceeds 30 mass%, the Cr content in fume becomes extremely high, thereby the content of hexavalent chromium increases, and hexavalent chromium is not reduced sufficiently. Accordingly, Cr content is to be 11-30 mass%.
  • Si is added in the form of metal Si, Si oxide and/or Si compound.
  • the amount of these metal Si, Si oxide and Si compound is 0.5 mass% or above in total of respective amounts in terms of Si, the effect of amorphization can be secured.
  • the total of the amounts in terms of Si exceeds 4.0 mass%, the removability of slag deteriorates.
  • the amount to be added of these metal Si, Si oxide and Si compound is to be 0.5-4.0 mass% in total of respective amounts in terms of Si, preferably 1.0-4.0 mass%.
  • the metal Si included in the outer sheath, the metal Si, silica sand, feldspar, potassium fluoride and the like in the added raw material of the flux can be cited. All these raw materials are effective in increasing SiO 2 in fume, and the effect of reducing hexavalent chromium can be secured in any of these adding raw materials.
  • Alkaline metals including Na, K and Li react with Cr in fume and form a hexavalent chromium compound soluble in water such as sodium chromate for example. Therefore, by increasing the alkaline metals in fume, the hexavalent chromium content in fume increases. Accordingly, the amount of the Na compound, K compound and Li compound is to be 0.50 mass% or below in total of each of an amount in terms of Na, an amount in terms of K and an amount in terms of Li. More preferable range of the amount of the Na compound, K compound and Li compound is 0.30 mass% or below in total of the amounts in terms of respective elements. Also, as the sources of Na, K and Li, oxides, fluorides and the like thereof can be cited.
  • the fluorine compound is to be 0.01-1.0 mass% in terms of F, and more preferably 0.01-0.80 mass%.
  • a parameter expressed by Na + K + Li ⁇ Cr 2 / Si + 4.7 ⁇ F is to be 10 or below.
  • the present inventors found out that there was a strong correlation between the parameter and the hexavalent chromium amount in fume. Also, by making the parameter 10 or below, hexavalent chromium in fume can be greatly reduced in both cases that the shield gas is 100% CO 2 and a gas mixture (80% Ar-20% CO 2 ).
  • the elements appearing in the denominator are factors contributing more to reducing hexavalent chromium in fume when they are bigger, and the elements appearing in the numerator are factors contributing more to reducing hexavalent chromium in fume when they are smaller.
  • the parameter is an indicator obtained by experimentally studying the balance of the two factors.
  • TiO 2 has an effect of stabilizing an arc in addition to an effect of improving slag covering, and is effective in improving the arc stability when the alkaline metals are reduced.
  • TiO 2 is added by 1.5 mass% or above, preferably 2.0 mass% or above.
  • TiO 2 is to be 8.0 mass% or below.
  • ZrO 2 and Al 2 O 3 are raw materials added as slag forming agents. For the purpose, ZrO 2 and Al 2 O 3 are added by 0.1 mass% or above in total.
  • the amount to be added is to be 3.2 mass% or below in total, preferably 2.7 mass% or below.
  • the sources for TiO 2 rutile, ilmenite, titanium oxide, potassium titanate and the like can be cited, and these raw materials are added solely or combining two kinds or more.
  • the sources for ZrO 2 zirconium sand, zirconium oxide and the like can be cited.
  • Ni, Mo, Mn and Fe are contained by 50-80 mass% in total. Not only that Ni, Mo, Mn and Fe are included in the outer sheath, they are added to the flux as metal powder.
  • the other oxides Al 2 O 3 and MgO can be cited.
  • Table 1 and Table 2 below illustrate the composition of the flux-cored wires of the examples and the comparative examples.
  • the fume was taken by a method of performing welding for five minutes continuously in accordance with JIS Z 3930:2001 (Determination of emission rate of particulate fume in arc welding) and taking the fume generated during the welding by a filter.
  • the welding condition was 200 A of the welding current and 30 V of the arc voltage.
  • hexavalent chromium included therein was analyzed.
  • the analytical method for hexavalent chromium in fume was in accordance with ISO 16740:2005.
  • the analytical results of the hexavalent chromium and the weldability in welding are shown in Table 3 below.
  • the stability of transfer of the molten droplet and the generated amount of the spatter were organoleptically evaluated.
  • One that greatly generated coarse droplets transfer and the spatter was evaluated to be unstable in an arc.
  • the slag removability one in which the slag was naturally removed after welding without seizure of slag was determined to be excellent.
  • the amount of hexavalent chromium in fume was 500 ppm or below, it was determined that there was an effect of reducing the amount of hexavalent chromium in fume. Further, the generated amount of the fume was also measured. As a result of it, in all of the examples 1 to 9 of the present invention, the amount of hexavalent chromium is 500 ppm or below, and it is known that the amount of hexavalent chromium can be reduced. On the other hand, in the cases of the comparative examples, the amount of hexavalent chromium exceeded 500 ppm with the exception of the comparative examples 2, 8, 10 and 11.
  • the weldability was as poor as not reaching a practical level.
  • the value of the parameter did not satisfy the required range, and the amount of hexavalent chromium in fume became high.
  • the comparative example 2 because Si was too high, although the amount of hexavalent chromium became low, the slag removability deteriorated to a large extent.
  • the comparative examples 3 to 6 because the added amount of the alkaline metals was too much, the value of the parameter did not satisfy the required range, and the amount of hexavalent chromium became high.
  • the comparative example 7 because F was too low, the pit resistance deteriorated.
  • Table 4 shows the composition of the welding wire used. Also, the relation between the value of the parameter ⁇ ([Na]+[K]+[Li]) ⁇ [Cr] 2 ⁇ /([Si]+4.7 ⁇ [F]) and the amount of hexavalent chromium in fume is shown in Table 5 below and FIG. 1 .
EP12000432.0A 2011-03-01 2012-01-24 Stainless steel flux-cored wire Active EP2495066B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011043648A JP5410466B2 (ja) 2011-03-01 2011-03-01 ステンレス鋼フラックス入りワイヤ

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EP2495066A1 EP2495066A1 (en) 2012-09-05
EP2495066B1 true EP2495066B1 (en) 2017-12-13

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EP (1) EP2495066B1 (ja)
JP (1) JP5410466B2 (ja)
CA (1) CA2763150C (ja)

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JP2012179626A (ja) 2012-09-20
EP2495066A1 (en) 2012-09-05
CA2763150A1 (en) 2012-09-01
US20120223064A1 (en) 2012-09-06
JP5410466B2 (ja) 2014-02-05
US10369666B2 (en) 2019-08-06

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